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Graphene oxide/epoxy composite coatings have attracted much attention from researchers due to their excellent anti-corrosion properties. Graphene oxide as a two-dimensional nano-filler can enhance the overall properties of epoxy resin coatings. In the paper, models of graphene oxide/epoxy composite coatings with different permeation degrees are constructed respectively. The interfacial interaction between GO and epoxy resin and the adsorption properties of epoxy coating with metal are analyzed from an atomic perspective by molecular dynamics simulations. The results indicate that the interfacial adsorption effect of the epoxy coating on the protected metal is stronger than the interfacial bonding of GO on the epoxy resin matrix. Simulations of models with different degrees of permeation suggest that the permeation of the NaCl solution occupies the interfacial space and reduces the adhesion between the two interfaces.